Sterilant composition

ABSTRACT

A biocidal, aqueous composition for killing bacteria, spores, fungi, and viruses on nonabsorbent surfaces comprises at least one quaternary ammonium compound, at least one aliphatic dialdehyde having from two to six carbon atoms, and at least one aliphatic hydroxyl compound having form one to eight carbon atoms. 
     This sterilant is stable for weeks, is especially useful between pH 4 to 9, and may additionally comprise a chelating agent.

RELATED U.S. APPLICATIONS

This is a divisional application of continuation application Ser. No. 08/164,002, filed Dec. 8, 1993, issued as U.S. Pat. No. 5,344,838 on Sep. 6, 1994, which is a continuation of application Ser. No. 07/866,010, filed Apr. 9, 1992, now abandoned, which is a continuation of application Ser. No. 758,400, filed Aug. 27, 1991, which has matured into U.S. Pat. No. 5,124,359, granted Jun. 23, 1992 which is a continuation-in-part of Ser. No. 210,626 filed Jun. 23, 1988 which has matured into U.S. Pat. No. 4,923,899, granted May 8, 1990, which is a continuation-in-part of Ser. No. 139,166 filed Dec. 22, 1987 now abandoned which is a continuation of Ser. No. 906,557 filed Sep. 8, 1986; now abandoned which is a continuation of Ser. No. 776,479 filed Sep. 16, 1985, now abandoned which is a continuation-in-part of Ser. No. 692,776 filed January 18, 1985 now abandoned.

FIELD OF THE INVENTION

This invention relates to a broad-spectrum biocidal composition effective for the rapid killing of a wide variety of bacteria, spores, fungi, and viruses on a wide variety of nonabsorbent surfaces such as metals, plastics, resins, woods, rubbers, ceramics, and glasses. The composition of the present invention kills so many organisms on such a wide variety of surfaces that it may be termed a sterilant.

Some of the articles which may be sterilized by the composition of the present invention are counters, floors, sheets, catheters, dialysis machine tubing, anesthetic breathing bags, surgical instruments, dental bite blocks, saliva-draining tubes, respirator equipment, and environmental surfaces in general.

BACKGROUND OF THE INVENTION

In the past in medical and dental circles, steam sterilization or treatment with ethylene oxide in a closed apparatus have been considered ideal ways of sterilizing equipment. But for many types or parts of apparatus, steam sterilization is impractical because of the size or number of items to be sterilized. For parts of equipment which actually come in contact with the patient, such as dental bite blocks, anesthetic breathing bags, respirators, etc. it is impermissible for ethylene oxide to be used because residual trace amounts might harm the patient.

Hence, a stable, benign, broad-spectrum sterilant effective at a wide range of pH's is greatly desired by the medical/dental profession for environmental use, especially on nonabsorbent surfaces.

A disinfectant is generally considered to be an agent which destroys bacterial organisms which are growing, but not bacterial spores. Germicide and bactericide are approximately synonymous with disinfectant. An antiseptic inhibits the growth of microorganisms. A sporicide kills spores of fungi molds, and bacteria. Since spores are more resistant than bacteria, sporicides are generally considered sterilizing agents. Biocides kill all living microorganisms, hence also are sterilizing agents. A virucide kills viruses; a fungicide kills fungi. The novel sterilant of this invention kills bacteria, spores, fungi and viruses. Hence, it may be termed a biocide or a sterilant.

The Hamilton U.S. Pat. No. 3,208,936, discloses combining a broad range of quaternary amines as germicides and foaming agents in recirculation type toilets.

The Halley U.S. Pat. No. 3,785,971, is directed to a waste treatment material for a storage holding tank in which paraformaldehyde and an alkali carbonate or hydroxide are combined.

U.S. Pat. No. 2,998,390, granted Aug. 29, 1961 to Hamilton and U.S. Pat. No. 3,107,216, granted Oct. 15, 1963 to Hamilton, disclose a recirculating toilet fluid which contains a quaternary ammonium salt.

"Quaternary Ammonium Salts as Germicidals. Nonacylated Quaternary Ammonium Salts Derived from Aliphatic Amines," Shelton, R. S. et al., Journal of the American Chemical Society, vol. 68, pp. 753-55 (1946), reported that alkyl quaternary ammonium salts have germicidal powers and N-benzyl substitutes do not affect this germical activity.

It was reported in Gardner, J. Disinfection, Sterilization & Preservation, p. 900, S. S. Block, ed., Lea & Febiger, 2nd ed. (1977) to include chelating agents with phenols and certain quaternary ammonium salts for enhanced activity against Gram-negative bacteria.

The Schattner U.S. Pat. No. 4,103,001 discloses an aqueous mixture of phenol, sodium tetraborate, and sodium phenate solution to which is added aqueous glutaraldehyde in order to kill some bacteria and bacterial spores. This mixture cannot be used against fungi or viruses.

The Stonehill U.S. Pat. No. 3,282,775 discloses a mixture of dialdehydes and a cationic surface active agent, plus a lower alcohol, which kills four spore-forming bacteria, but not fungi or viruses.

The Pepper U.S. Pat. No. 3,016,328 discloses that simple dialdehydes plus a lower alkanol to the extent of about 60 to 70% and an alkalinizing agent to yield a pH range of about 8 to 9.5 kill four spore-forming bacteria, two of which are the same as in U.S. Pat. No. 3,282,775.

Borick, et al in the Journal of Pharmaceutical Sciences, Vol. 53, No. 10 at p. 1273 disclose that glutaraldehyde alkalinized with sodium bicarbonate kills eight nonspore-forming bacteria, four spore-forming bacteria, one fungus, and nine viruses, but that this alkaline solution was stable only for about two weeks.

French Patent 2,321,300 discloses that a mixture of aldehyde and quaternary ammonium compound has antiseptic properties by reducing the growth of five bacteria of interest to the food industry.

British Patent 1,443,786 discloses that a mixture of glutaraldehyde, a lower alcohol, and a highly ionizable salt at acidic pH ranges kills four sporulating bacteria by ion-exchange with the calcium in the walls of the bacterial spores.

The Wagner U.S. Pat. No. 4,107,312 discloses a disinfectant mixture of a strong formaldehyde solution, plus minor amounts of glyoxal and glutaraldehyde, plus a quaternary ammonium salt, methanol to stabilize the formaldehyde, a nonionic wetting agent, optionally some alcohol or glycol, and a scent, all at a neutral pH in order to avoid corrosion of aluminum toilets (or minimize corrosion of magnesium toilets) in aircraft.

The Mandt U.S. Pat. No. 4,444,785 discloses a disinfecting solution for soft contact lenses against two nonsporulating bacteria comprising a very low concentration of 1,5 pentanedial at neutral pH compatible with the human eye.

The Schaeufele U.S. Pat. No. 4,320,147 discloses a germicidal composition comprising quaternary ammonium chlorides, plus builder salts, which are useful for disinfection against bacteria.

Canadian Patent No. 1,154,555 discloses a bactericide composition containing formaldehyde, glutaraldehyde and a quaternary ammonium ingredient.

French Patent No. 2,145,444 discloses a bactericide composition containing formaldehyde and a quaternary ammonium compound.

The Lockwood U.S. Pat. No. 3,505,690 relates to a disinfectant dispersing system.

The Buchalter U.S. Pat. No. 3,983,252 discloses a chemical disinfecting composition comprising a dialdehyde and an alkali metal salt of a hydrocarbon carboxylic acid and optionally an alcohol.

The Goldhaft U.S. Pat. No. 4,022,911 discloses a disinfectant composition comprising three essential active ingredients, namely a dimethyl quaternary ammonium halide salt, a phenol or derivative thereof, and formaldehyde.

Oshchepkova and Kochkin in the Proceedings of the First All-Union Conference on Biocorrosion, Biodamage, and Marine Encrustation (1975), C.A.91:69799p report that a mixture of organotin fumarates or acryloyloxy stannate mixed with N-alkyl pyridinium salts or tetraalkylammonium salts protect wood samples in water from two common bacteria--A.niger and P. purpureum.

OBJECTS OF THE INVENTION

It is an object of this invention to provide a stable, benign, nonodorous, solution which kills a broad-spectrum of bacteria, spores, fungi, and viruses rapidly at a wide range of pH.

It is a further object of this invention to provide a broad-spectrum sterilant which will remain an active solution for at least several weeks.

It is yet another object of this invention to provide a sterilant which is effective on hard, nonabsorbent, "environmental" surfaces such as anesthetic breathing bags, dialysis tubing, respirators, dental bite blocks, saliva-draining tubes, and the like for which sterilization by steam or ethylene oxide is either impractical or physiologically disfavored.

It is an object of the present invention to provide a sterilant composition effective for killing rapidly individual microorganisms or a combination of several different kinds of microorganisms, such as bacteria, spores, fungi and/or viruses.

Another object of the invention is to provide a sterilant for a wide variety of hard surfaces such as metals, plastics, resins, rubbers, ceramics, and glasses.

Yet another object of the present invention is to provide a sterilant which is effective in the presence of high concentrations of blood, sputum, feces, urine, vomitus, and other animal exudates.

Other objects of the present invention will be apparent to those skilled in the art.

SUMMARY OF THE INVENTION

Surprisingly, a broad-spectrum sterilant capable of rapidly killing bacteria, sporulating bacteria, spores, fungi, and viruses can be achieved by combining in an aqueous solution an effective amount of at least one quaternary ammonium compound, at least one aliphatic dialdehyde having from two to six carbon atoms, and at least one aliphatic hydroxyl compound having from one to eight carbon atoms.

Another aspect of the invention relates to the use of the novel sterilant on "hard" or "environmental" surfaces (nonabsorbing) such as medical or dental equipment for which previously steam sterilization or treatment with ethylene oxide were employed.

The sterilant of the present invention relates to a liquid composition which is effective for rapidly killing at least one microorganism or any combination of two or more different microorganisms such as bacteria, spores, fungi and viruses.

For still another aspect of the invention, the novel sterilant is employed over a wide range of pH and is stable for several weeks after having been compounded.

Yet another aspect of the present invention arises from its efficacy in the presence of high concentrations of blood, sputum, urine, feces, vomitus or other bodily liquids or suspensions.

A further aspect of the present invention is its efficacy in sterilizing hard surfaces of metals, plastics, rubbers, resins, wood, ceramics, or glasses.

A typical embodiment of the invention comprises:

    ______________________________________                                         Component               Weight %                                               ______________________________________                                         Alkylbenzyldimethylammonium chloride                                                                   0.1                                                    Cetyldimethylethylammonium bromide                                                                     0.1                                                    Glutaraldehyde          2.6                                                    Isopropyl alcohol       0.2                                                    Propylene glycol        0.16                                                   Sodium nitrite          0.11                                                   Tetrasodium ethylenediamine tetraacetate                                                               0.015                                                  Water                   balance                                                ______________________________________                                    

Processes for employing these sterilant compositions are also disclosed herein.

DETAILED DESCRIPTION OF THE INVENTION

As discussed above, the prior art discloses individual compounds or mixtures of compounds which kill or inhibit the growth of a narrow range of organisms such as some bacteria, spores, fungi, or viruses. The synergistic combination of the seven components of the present invention unexpectedly kills all types of the names organisms, hence it is a sterilant. Among the classes of organisms killed by the composition of the present invention alone or admixed together are Gram-negative bacteria, Gram-positive bacteria, algae, protozoa, Gram-positive spore-forming bacteria, fungi, and many types of viruses.

Among the many typos of viruses killed by the composition of the present invention are:

orbiviruses, orthomyxoviruses, papovaviruses, paramyxoviruses, parvoviruses, picornaviruses, poxviruses, coronaviruses, flaviviruses, herpesviruses, adenoviruses, arenaviruses, bunyaviridae, caliciviruses, reoviruses, retioviruses, rhabdoviruses, rotaviruses, togaviruses, and various unclassified viruses, plus plant viruses.

In addition to the bacteria, spores, protozoa, algae, fungi, and viruses categorized above, the composition of the present invention can kill alone or in combination with the other organisms typified above various miscellaneous organisms from the Chlamydia Coxiella, Ehrlichia, Rickettsia, Rochalimaea, Wolbachia, and Thai tick typhus.

It is to be emphasized that the composition of the present invention is a sterilant which can kill any or all of the types of organisms described here alone or in any combination.

At the end of the Examples of this specification and before the claims, several hundred representative specific organisms are listed in Tables I to VII on which the synergistic composition of the present invention is effective.

The cationic, quaternary salts useful in the present invention may contain either or both of aliphatic and aromatic moieties. Although quaternary ammonium salts are preferred, cationic phosphonium, or sulfonium, or any other positive nonmetallic nuclei may be selected. Some of the aliphatic or alicyclic substituents for the quaternary ions are alkyl groups containing one to 30 carbon atoms both linear and branched, alkoxy groups also containing one to 30 carbon atoms both linear and branched, alicyclic groups such as cyclohexyl and its alkylated or alkyloxylated derivatives, and halogenated alkyl, halogenated alicyclic, or halogenated alkyloxy derivatives.

Aromatic moieties, which may themselves be substituted by aliphatic, alicyclic, alkyloxy groups, useful as substituents for the quaternary cationic salts of the present invention are benzyl, tolyl, xylyl, naphthyl, pyridyl, benzal, quinolyl and the like.

More specifically, some aliphatic quaternary ammonium salts which are useful in the present invention are:

tetramethyl ammonium halide, trimethylethyl ammonium halide, dimethyldiethyl ammonium halide, methyltriethyl ammonium halide, tetraethyl ammonium halide, cetyldimethylethyl ammonium halide, trimethyln-propyl ammonium halide, dimethyldin-propyl ammonium halide, methyltrin-propyl ammonium halide, tetran-propyl ammonium halide, methylethyln-propyln-butyl ammonium halide, ethyln-propyln-pentyl ammonium halide, trimethylallyl ammonium halide, dimethyldiallyl ammonium halide, methyltriallyl ammonium halide, tetraallyl ammonium halide, N,N,N,N',N',N'-hexaethyl-1,2-ethylene diammoniumhalide, N,N,N,N',N',N'-hexaethyl-1,4-butylenediammonium halide, N,N,N'-dibenzyl-N,N,N',N', tetramethyl-1,2-ethylene diammonium halide, N,N'-di(4-chlorobenzyl)-N,N,N',N'-tetramethyl-1,2-ethylenediammoniumhalide, N,N,N'-tetraethyl-N,n"-dioctadecyl-1,2-ethylene diammonium halide, N,N,N',N'-tetraethyl-N,N'-dihexadecyl-1,4-butylene diammonium halide, octadecyltrimethyl ammonium halide, dioctadecyldimethyl ammonium halide, trioctadecylmethyl ammonium halide tetraoctadecyl ammonium halide, hexadecyltriethyl ammonium halide, hexadecyldimethylethyl ammonium halide, hexadecyldiethylmethyl ammonium halide, didecyldioctyl ammonium halide, didecyldihexyl ammonium halide, and hexyloctyldecyldodecyl ammonium halide.

Some representative useful quaternary ammonium salts containing an aromatic moiety include:

benzylodecyldimethyl ammonium halide, o-tolyldodecyldimethyl ammonium halide, m-tolyldodecyldimethyl ammonium halide, p-tolyldodecyldimethyl ammonium halide, 2,3-xylyldodecyldimethyl ammonium halide, 2,4-xylydodecyldimethyl ammonium halide, 2,5-xylyldodecyldimethyl ammonium halide, 3,4-xylyldodecyldimethyl ammonium halide, 3,5-xylyldodecyldimethyl ammoniuim halide, 2-chlorobenzyldodecyldimethyl ammonium halide, 3-chlorobenzyldodecyldimethyl ammonium halide, 4-chlorobenzyldodecyldimethyl ammonium halide, 2,3-dichlorobenzyldodecyldimethyl ammonium halide, 2,4-dichlorobenzyldodecyldimethyl ammonium halide, 2,5-dichlorobenzyldodecyldimethyl ammonium halide, 2,6-dichlorobenzyldodecyldimethyl ammonium halide, 3,4-dichlorobenzyldodecyldimethyl ammonium halide, 3,5-dichlorobenzyldodecyldimethyl ammonium halide, 2-nitrobenzyldodecyldimethyl ammonium halide, 3-nitrobenzyldodecyldimethyl ammonium halide, 4-nitrobenzyldodecyldimethyl ammonium halide, 2,4-dinitrobenzyldodecyldimethyl ammonium halide, 3,5-dinitrobenzyldodecyldimethyl ammonium halide, 2-sulfobenzyldodecyldimethyl ammonium halide, 3-sulfobenzyldodecyldimethyl ammonium halide, 4-sulfobenzyldodecyldimethyl ammonium halide, 2-carboxybenzyldodecyldimethyl ammonium halide, 3-carboxybenzyldodecyldimethyl ammonium halide, 4-carboxybenzyldodecyldimethyl ammonium halide, benzylhexyldimethyl ammonium halide, benzyloctyldimethyl ammonium halide, benzyldecyldimethyl ammonium halide, benzyldodecyldimethyl ammonium halide, benzyltetradecyldimethyl ammonium halide, benzylhexadecyldimethyl ammonium halide, benzyloctadecyldimethyl ammonium halide.

Some representative, useful quaternary ammonium salts containing heterocyclic, aromatic moieties include:

n-hexylpyridinium halide, n-octylpyridinium halide, n-decylpyridinium halide, n-dodecylpyridinium halide, n-tetradecylpyridinium halide, n-hexadecylpyridinium halide, n-hexyllutidinium halide, n-octyllutidinium halide, n-decyllutidinium halide, n-dodecyllutidinium halide, n-tetradecyllutidinium halide, n-hexadecyllutidinium halide, n-hexylpicolinium halide, n-octylpicolinium halide, n-decylpicolinium halide, n-dodecylpicolinium halide, n-tetradecylpicolinium halide, n-hexadecylpicolinium halide, n-hexylquinolinium halide, n-octylquinolinium halide, n-decylquinolinium halide, n-dodecylquinolinium halide, n-tetradecylquinolinium halide, n-hexadecylquinolinium halide, n-hexylisoquinolinium halide, n-octylisoquinolinium halide, n-decylisoquinolinium halide, n-dodecylisoquinolinium halide, n-tetradecylisoquinol inium halide, n-hexadecylisoquinolinium halide, n-hexylquinazolinium halide, n-octylquinazolinium halide, n-decylquinazolinium halide, n-dodecylquinazolinium halide, n-tetradecylquinazolinium halide, n-hexadecylquinazolinium halide, n-hexylquinoxalinium halide, n-octylquinoxalinium halide, n-decylquinoxalinium halide, n-dodecylquinoxalinium halide, n-tetradecylquinoxalinium halide, n-hexadecylquinoxalinium halide, n-hexylpyridopyridinium halide, n-octylpyridopyridinium halide, n-decylpyridopyridinium halide, n-dodecylpyridopyridinium halide, n-tetradecylpyridopyridininum halide, and n-hexadecylpyridopyridinium halide.

The preferred counter ions for the quaternary cationic salts are halides, especially chloride and bromide. Particularly useful for practicing the present invention are alkylbenzyldimethyl ammonium chlorides, wherein the alkyl groups contain between 10 and 18 carbon atoms, and cetyldimethylethyl ammonium bromide. The useful range of quaternary cationic salts in an effective amount of sterilant is from about 0.05% to 3% in actual use by weight.

Other counter ions, anions, useful in the practice of the present invention to neutralize the positive charge of the ammonium, phosphonium, sulfonium, or other positive moieties can be found in the following list bicarbonate, bisulfite, fluoride, borate, carbonate, nitrite, nitrate, phosphite, phosphate, sulfite, sulfate, chloride, hypochlorite, chlorite, chlorate, perchlorate, hydroxide, fluoborate, iodide, iodate, periodate, and bromate.

The solubility of the various solutes in the novel sterilant of the instant invention is improved by using small amounts of alkanols having from one to six carbon atoms and/or glycols having from two to four carbon atoms. These alkanols and glycols also have concomitant and peripheral biocidal effect. Especially useful alkanols are methanol, ethanol, and isopropyl alcohol. Especially useful polyols are glycols such as ethylene glycol, propylene glycol, diethylene glycol, as well as glycerine. In the diluted solution for actual use, the effective amount for the alkanol is from about 0.1% to 3% by weight, and the effective amount for the polyol or glycol is from about 0.1% to 3% by weight.

Other alcohols having eight or less carbon atoms useful in the practice of the present invention are:

1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 2-methyl-3-butanol, 2-methyl-4-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,2-dimethyl-3-butanol, 2,2-dimethyl-4-butanol, 2,3-dimethyl-2-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 2-methyl-4-pentanol, 2-methyl-5-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 2,2-diethyl-1-ethanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2,2,3-trimethyl-3-butanol, 2,3-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol, 3-ethyl-1-pentanol, 3-ethyl-2-pentanol, 3-ethyl-3-pentanol, 4-ethyl-1-pentanol, 4-ethyl-2-pentanol, 4-ethyl-3-pentanol, 2-ethyl-1-pentanol, 2-methyl-1-hexanol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, 3-methyl-3-hexanol, 3-methyl-4-hexanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol, 5-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-methyl-2-heptanol, 3-methyl-2-heptanol, 4-methyl-2-heptanol, 5-methyl-2-heptanol, 6-methyl-2-heptanol, 2-methyl-3-heptanol, 3-methyl-3-heptanol, 4-methyl-3-heptanol, 5-methyl-3-heptanol, 6-methyl-3-heptanol, 2-methyl-4-heptanol, 3-methyl-4-heptanol, 4-methyl-4-heptanol, 5-methyl-4-heptanol, 6-methyl-4-heptanol, 2,2-dimethyl-1-hexanol, 3,3-dimethyl-1-hexanol, 4,4-dimethyl-1-hexanol, 5,5 -dimethyl-1-hexanol, 2,3-dimethyl-1-hexanol, 2,4-dimethyl-1-hexanol, 2,5-dimethyl-1-hexanol, 3,4-dimethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl-1-hexanol, and 5-ethyl-1-hexanol.

Other glycols having eight or less carbon atoms useful in the practice of the present invention are:

1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2,methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,2-butanediol, 2-methyl-1,3-butanediol, 2-methyl-1,4-butanediol, 2-methyl-2,3-butanediol, 2-methyl-3,4-butanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2-methyl-1,2-pentanediol, 2-methyl-1,3-pentanediol, 2-methyl-1,4-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-2,3-pentanediol, 2-methyl-2,3-pentanediol, 2-methyl-2,4-pentanediol, 2-methyl-2,5-pentanediol, 2-methyl-3,4-pentanediol, 2-methyl-3,5-pentanediol, 2-methyl-4,5-pentanediol, 2,3-dimethyl-1,2-butanediol, 2,3-dimethyl-1,3-butanediol, 2,3-dimethyl-1,4-butanediol, 2,3-dimethyl-2,3-butanediol.

Certain salts with anions at less than full oxidation state, such as nitrite, bisulfite, or chlorite, may be optionally employed in the novel sterilant solution of the instant invention to prevent corrosion, as well as for their biocidal activity.

Also useful in the practice of the present invention are cations wherein the metal oxidation state is lower than its chemically possible maximum.

Some useful compounds with less than full oxidation states are found in the following salts first some with reduced anions and then some salts with less oxidized cations, as follows:

sodium phosphite, sodium sulfite, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium selenite, sodium arsenite, sodium hypobromite, sodium bromite, sodium bromate, sodium stannite, sodium antimonite, sodium tellurite, sodium ferrocyanide, sodium manganite, sodium manganate, potassium phosphite, potassium, sulfite, potassium hypochorite, potassium chlorite, potassium chlorate, potassium selenite, potassium arsenite, potassium hypobromite, potassium bromite, potassium bromate, potassium stannite, potassium antimonite, potassium tellurite, potassium ferrocyanide, potassium manganite, potassium manganate, lithium phosphite, lithium sulfite, lithium hypochlorite, lithium chlorite, lithium chlorate, lithium selenite, lithium arsenite, lithium hypobromite, lithium bromite, lithium bromate, lithium stannite, lithium antimonite, lithium antimonite, lithium tellurite, lithium ferrocyanide, lithium manganite, lithium manganate, rubidium nitrite, rubidium phosphate, rubidium sulfite, rubidium hypochlorite, rubidium chlorite, rubidium chlorate, rubidium selenite, rubidium arsenite, rubidium hypobromite, rubidium bromite, rubidium bromate, rubidium stannite, rubidium antimonite, rubidium tellurite, rubidium ferrocyanide, rubidium manganite, rubidium manganate, cesium nitrite, cesium phosphite, cesium sulfite, cesium hypochlorite, cesium chlorite, cesium chlorate, cesium selenite, cesium arsenite, cesium hypobromite, cesium bromite, cesium bromate, cesium stannite, cesium antimonite, cesium telurite, cessium ferrocyanide, cesium manganite, cesium manganate, ferrous ferrocyanide, ferrous ferricyanide, cuprous chloride,

ferrous phosphate, stannous chloride, ferrous sulfate, manganous sulfate, plumbous sulfate, and chromous chloride.

Particularly useful are sodium, potassium, lithium, and ammonium salts of nitrite, bisulfite, and chlorite; especially useful is sodium nitrite. These optional salts may be employed in the range from 0.05% to about 2.0% by weight of the actual solution employed.

A chelating agent may be optionally employed in the broad-spectrum sterilant of the present invention from 0% to 0.025% by weight to aid in solubility of the other components, to counteract any deleterious effects from diluting concentrated commercial strengths with hard water for use, and to help break down the coatings of spores, which have a high concentration of multivalent ions. The preferred chelating agent to practice the current invention may range from 0% to 0.025% by weight and is ethylene diamine tetraacetic acid (EDTA). Partial esters or salts of EDTA may also be used. An example of a salt of EDTA is tetrasodium ethylenediamine tetraacetate.

Other useful chelating agents may be found in the following acids, full salts, or partial salts of:

oxalic acid, malonic acid, oxaldihydrixamic acid, diaminoglyoxime, dithiomalonic acid, glyoxime, maleic acid, fumaric acid, oxalacetic acid, diglycolic acid, tartaric acid, oxalenediuramidoxime, thiodiglycolic acid, iminodiacetic acid, nitrilotriacetic acid, dimethylglyoxime, hydrazine-N,N'-diacetic acid, citraconic acid, itaconic acid, 2,4-pentanedione, glutaric acid, N-methyliminodiacetic acid, glutamic acid, aconitric acid (trans), gluconic acid, 1,2-cyclohexanediamine-N,N,N'-tetraacetic acid (cis&trans), 1,2-ethylenediamine-N,N,N',N'-tetraacetic acid, N'-benzylethylenediamine-N,N,N'-triacetic acid, diethylenetriamine-N,N,N',N",N"-pentaacetic acid, hexamethyldiamine-N,N,N',N'-tetraacetic acid, 2,2"-ethylenedioxybis(ethyliminodiacetic acid), 2,2'-oxybis (propyliminodiacetic acid), triethylenetetraminehexaacetic acid, 1,3,5-triaminocyclohexanehexaacetic acid, and ethyl acetoacetate.

A dialdehyde containing up to six carbon atoms is a component of the broad-spectrum sterilant of the present invention. Dialdehydes include malonaldehyde, succinaldehyde, oxaldehyde (glyoxal), adipaldehyde, and preferably glutaraldehyde. Alternatively, these compounds may be termed aliphatic dials, e.g. 1,5 pentanedial. By themselves, these compounds are effective germicides to some degree, at high pH, but they fail to have the wide breadth and speed of killing of the mixture of the current invention. This is especially true for the killing of the sporulent bacteria, where the dialdehydes alone can take up to ten hours to kill spores, and for many viruses, where dialdehydes are ineffective. In the final dilution as used, in the present invention, an effective amount of the dialdehyde is from about 0.5% to about 7% by weight. A concentration of dialdehyde of about 2.6 to 5 weight % is preferred and a concentration of dialdehyde of 3.2 weight % is especially preferred.

Some useful dialdehydes in the practice of the present invention are the following compounds and their mixtures:

1,2-ethanedial, 1,3-propanedial, 1,4-butanedial, 1,5-pentanedial, 2-methyl-1,4-butanedial, 2-methyl-1,3-propanedial, 2,2-dimethyl-1,3-propanedial, 2,3-dimethyl-1,4-butanedial, 2,2-dimethyl-1,4-butanedial, 1,6 hexanedial, 2-methyl-1,5-pentanedial, 3-methyl-1,5-pentanedial, 2-ethyl-1,3-propanedial, and Z-N-propylpropanedial. Some examples of heterocyclic dialdehydes are

furan-2,5-dialdehyde, furan-3,4-dialdehyde, thiophene-2,5-dialdehyde, thiophene-3,4-dialdehyde, pyrrole-2,5-dialdehyde, pyrrole-3,4-dialdehyde, imidazole-4,5-dialdehyde, pyrazole-3,4-dialdehyde, 1,2,3-triazole-4,5-dialdehyde, pyrazine-2,3-dialdehyde, pyrimidine-4,5-dialdehyde, pyridazine-3,4-dialdehyde, pyridazine-4,5-dialdehyde. Aliphatic dialdehydes are preferred, but heterocyclic dialdehydes such as those named above may also be employed.

As a practical matter, it is preferred to produce the broad-spectrum sterilant of the present invention in the form of one or more concentrated solutions prior to transport and storage. The concentrations of these solutions would be 50 to 100-fold higher strength than the actual use-strengths given above. After transport and storage, the user, normally a medical or dental technician, will dilute the concentrate to produce an effective amount at the ultimate dilution and then add the dialdehyde.

In concentrated form, a preferred embodiment of the sterilant concentrate of the present invention would have the following approximate concentrations by weight:

    ______________________________________                                                                Weight %                                                ______________________________________                                         Alkyl*benzyldimethylammonium chloride                                                                   7                                                     *50% C-12, 30% C-14, 17% C-16, 3% C-18                                         Cetyldimethylethylammonium bromide                                                                      7                                                     Isopropyl alcohol        14                                                    Propylene glycol         12                                                    Sodium nitrite           7                                                     EDTA                     1.5                                                   Water, balance up to 100%                                                      ______________________________________                                    

In actual practice, the user will have prepared a desired quantity of the diluted sterilant concentrate by diluting the sterilant concentrate with distilled or tap water. This resulting solution will serve, further, as the diluent for the dialdehyde concentrate then to be added thereto.

The diluted sterilant solution after combination is an exceptionally broad-spectrum sterilant on a wide variety of metal, plastic, cross-linked resin, rubber, composite, coated, painted or natural wood, ceramic, or glass non-adsorbent surfaces, exemplified by but not limited to the following: stainless steels (various), steels, not stainless (various), galvanized iron, copper, brass, aluminum, chromium plated metals, tinned plating metals, enameled metals, polyethylene, polypropylene, polystyrene, acrylics, polyacetals, nylons, "epoxy resin"-coated wood, polyurethane-coated wood, alkyd resin painted wood, alkyd resin-coated metal, oil-based painted wood, phenol-formaldehyde resin laminates ("Formica" type), polyvinyl chloride-based furniture surfaces ("Naugahyde" type), gum rubber surgical/dental adjuncts (dental dam, tubing, catheters, gloves), hard rubber devices (bite blocks), water-based, latex-painted wood, glazed porcelain and other ceramics and various types of glass such as lime, flint, and borosilicates.

The present invention will now be described by reference to the following examples, which are not to be deemed limitative of the present invention in any manner thereof.

EXAMPLE A

This example illustrates the preparation of an effective sterilizing amount of a final user solution of the sterilant composition of the invention.

A 15 ml ampule of the above sterilant concentrate was diluted with distiled water to a final volume of 1 liter. This was a dilution ratio of about 66.7:1. To this solution was added 50 ml of an aqueous 50% by weight solution of glutaraldehyde concentrate. On a weight basis, the concentration of glutaraldehyde will be about 2.6% in the final user solution.

Thus in the final user solution, the concentrations of the various components in the diluted sterilant will be as follows:

    ______________________________________                                                               Wt. %                                                    ______________________________________                                         Alkylbenzyldimethylammonium chloride                                                                   0.1                                                    Catyldimethylethylammonium bromide                                                                     0.1                                                    Isopropyl alcohol       0.2                                                    Propylene glycol        0.16                                                   Sodium nitrite          0.1                                                    EDTA                    0.02                                                   Dialdehyde, esp. glutaraldehyde                                                                        2.6                                                    Water                   balance                                                ______________________________________                                    

The diluted sterilant composition of the present invention may be employed over a wide, useful pH range from about pH 4 to about pH 9. The preferred range for use is from about pH 5 to about pH 8. This is in marked contrast to the use of alkalinized dialdehydes alone, which are effective only from about pH 7 to about pH 8.5. Although buffers may optionally be employed to keep the sterilant of the instant invention within a narrow pH range, no buffer is necessary to practice this invention.

EXAMPLE B

This example illustrates the preparation of an effective sterilizing amount of a final user solution of the sterilant composition of the invention.

A 15 ml ampule of the above sterilant concentrate was diluted with distilled water .to a final volume of 750 ml. This was a dilution ratio of about 50:1. To this solution was added 50 ml of an aqueous 50% by weight solution of glutaraldehyde concentrate. On a weight basis, the concentration of glutaraldehyde will be about 3.2% in the final user solution.

Thus, in the final user solution, the concentrations of the various components in the diluted sterilant will be as follows:

    ______________________________________                                                               Wt. %                                                    ______________________________________                                         Alkylbenzyldimethylammonium chloride                                                                   0.15                                                   Catyldimethylethylammonium bromide                                                                     0.15                                                   Isopropyl alcohol       0.25                                                   Propylene glycol        0.20                                                   Sodium nitrite          0.15                                                   EDTA                    0.025                                                  Dialdehyde, esp. glutaraldehyde                                                                        3.2                                                    Water                   balance                                                ______________________________________                                    

The diluted sterilant composition of the present invention may be employed over a wide, useful pH range from about pH 4 to about pH 9. The preferred range for use is from about pH 5 to about pH 8. This is in marked contrast to the use of alkalinized dialdehydes alone, which are effective only from about pH 7 to about pH 8.5. Although buffers may optionally be employed to keep the sterilant of the instant invention within a narrow pH range, no buffer is necessary to practice this invention.

EXAMPLE 1

This example illustrates the effectiveness of the sterilant composition of EXAMPLE A for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppm hard water as the diluent for test purposes:

    ______________________________________                                                               Wt. %                                                    ______________________________________                                         Alkylbenzyldimethylammonium chloride                                                                   0.1                                                    Catyldimethylethylammonium bromide                                                                     0.1                                                    Isopropyl alcohol       0.2                                                    Propylene glycol        0.16                                                   Sodium nitrite          0.11                                                   EDTA                    0.02                                                   Glutaraldehyde          2.60                                                   Water                   balance                                                ______________________________________                                    

Employing the Use-Dilution Method of the Association of Official Agricultural Chemists (AOAC) 60 ring carriers were tested on three batchs each for efficacy against the following organisms (US EPA Procedure DIS/TSS-1 and 2 of January 1982); Salmonella choleraesius ATCC 10708 (Gram-negative), Staphylococcus aureus ATCC 6538 (Gram-positive), and Pseudomonas aeruginosa ATCC 15442 (Gram-positive, nosocomial pathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 2

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 1 for testing against Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659 and Clostridium sporogenes ATCC 3584 employing US EPA Procedure DIS/TSS-9 of April 1981 (AOAC Sporicidal Test). Sixty carriers for each type of surface, porcelain penicylinders and silk suture loops, for each of three samples for each of three batches involved a total of 720 carriers.

As required, all microorganisms were killed on all carriers in about 5 hours, less than 6 hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard only after 10 hours of contact.

EXAMPLE 3

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 1 for testing against pathogenic fungus Trichophyton mentagrophytes ATCC 27289 according to the AOAC Fungicidal Test by EPA procedure DIS/TSS-6 of August 1981. For this fungus two batches were used for two samples each killing all organisms within 10 minutes at 20 degrees C.

EXAMPLE 4

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention in killing viruses, some of which none of the components of the novel sterilant can kill individually under the same conditions.

The novel sterilant solution was prepared as in EXAMPLE 1 for testing against the following viruses: Herpes Simplex I and II, Coxsackie virus B1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virus II, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, all according to EPA procedure DIS/TSSD-7. For two batches each, four replicates were carried by ten-fold dilution and measured to three-log diminution. After incubation, the samples were recovered after adsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20 degrees C. It is known that alkalinized glutaraldehyde fails to inactivate at least Coxsackie virus and Poliovirus I under these conditions.

EXAMPLE 5

This example illustrates the effectiveness of the sterilant composition of EXAMPLE B for nonsporulating bacteria.

The novel sterilant of the present invention was prepared with 400 ppm hard water as the diluent for test purposes:

    ______________________________________                                                               Wt. %                                                    ______________________________________                                         Alkylbenzyldimethylammonium chloride                                                                   0.15                                                   Catyldimethylethylammonium bromide                                                                     0.15                                                   Isopropyl alcohol       0.25                                                   Propylene glycol        0.20                                                   Sodium nitrite          0.15                                                   EDTA                    0.025                                                  Glutaraldehyde          3.2                                                    Water                   balance                                                ______________________________________                                    

Employing the Use-Dilution Method of the Association of Official Agricultural Chemists (AOAC) 60 ring carriers were tested on three batchs each for efficacy against the following organisms (US EPA Procedure DIS/TSS-1 and 2 of January 1982); Salmonella choleraesius ATCC 10708 (Gram-negative), Staphyllococcus aureus ATCC 6538 (Gram-positive), and Pseudomonas aeruginosa ATCC 15442 (Gram-positive, nosocomial pathogen).

All these microorganisms were killed within 10 minutes at 20 degrees C.

EXAMPLE 6

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention for killing sporulating bacteria.

The novel sterilant solution was prepared as in EXAMPLE 5 for testing against Gram-positive, sporulating bacteria Bacillus subtilus ATCC 19659 and Clostridium sporogenes ATCC 3584 employing US EPA Procedure DIS/TSS-9 of April 1981 (AOAC Sporicidal Test). Sixty carriers for each type of surface, porcelain penicylinders and silk suture loops, for each of three samples for each of three batches involved a total of 720 carriers.

As required, all microorganisms were killed on all carriers in about 5 hours, less than 6 hours at 20 degrees C.

In a similar test alkalinized glutaraldehyde can meet this standard only after 10 hours of contact.

EXAMPLE 7

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention for killing fungi and fungal spores.

The novel sterilant solution was prepared as in EXAMPLE 5 for testing against pathogenic fungus Trichophyton mentagrophytes ATCC 27289 according to the AOAC Fungicidal Test by EPA procedure DIB/TSS-6 of August 1981. For this fungus two batches were used for two samples each killing all organisms within 10 minutes at 20 degrees C.

EXAMPLE 8

This example illustrates the efficacy of the broad-spectrum sterilant of the present invention in killing viruses, some of which none of the components of the novel sterilant can kill individually under the same conditions.

The novel sterilant solution was prepared as in EXAMPLE 5 for testing against the following viruses: Herpes Simplex I and II, Coxsackie virus B1, Coxsackie virus A9, Vaccinia Virus, Influenza virus A, Adenos virus II, Poliovirus I, Rhino virus, Cytomegalo virus, and Corona virus, all according to EPA procedure DIS/TSSD-7. For two batches each, four replicates were carried by ten-fold dilution and measured to three-log diminution. After incubation, the samples were recovered after adsorption time on mammalian cell monolayers.

The novel sterilant inactivated all the viruses within 10 minutes at 20 degrees C. It is known that alkalinized glutaraldehyde fails to inactivate at least Coxsackie virus and Poliovirus I under these conditions.

The sterilant composition of the present invention has the advantages of being effective to kill a broad spectrum of microorganisms very rapidly with low concentrations of the active ingredients. The sterilant composition as a combination of ingredients is more effective against several microorganisms together at the same time than would be possible by using each active ingredient separately against the combination of microorganisms.

The sterilants of the disclosure above exemplified by the preferred embodiments of the various Examples are effective against a wide variety of microorganisms such as those of Tables I through VII.

                  TABLE I                                                          ______________________________________                                                 VIRUSES                                                                ______________________________________                                                 ADENOVIRUSES                                                                   Avian adenovirus Types 1-10                                                    Marble spleen disease virus                                                    Bovine adenovirus Types 1-8                                                    Canine adenovirus                                                              Infectious canine hepatitis                                                    Human adenovirus Types 1-41                                                    Mouse adenovirus                                                               Swine adenovirus                                                               Baboon adenovirus                                                              Chimpanzee adenovirus                                                          Simian adenovirus                                                              Types 1-39                                                                     ARENAVIRUSES                                                                   Anapari                                                                        Junin                                                                          Latino                                                                         Lymphocytic                                                                    choriomeningitis                                                               Bolivian Hemorrhagic Fever                                                     Parana                                                                         Pichinde virus                                                                 Tacaribe virus                                                                 Tamiami virus                                                                  BUNYAVIRIDAE                                                                   Anopheles Group                                                                Bunyamwera Super Group                                                         Bwamba Group                                                                   California Group                                                               Capim Group                                                                    Gamboa Group                                                                   Guama Group                                                                    Koongol Group                                                                  Patois Group                                                                   Simbu Group                                                                    Tete Group                                                                     Turlock Group                                                                  Phleboviruses                                                                  Nairoviruses                                                                   Hantaviruses                                                                   CALICIVIRUSES                                                                  Feline conjunctivitis                                                          Feline picornavirus                                                            Feline stonatitis                                                              CORONAVIRUSES                                                                  Calf diarrheal coronavirus                                                     Canine coronavirus                                                             Feline infectious                                                              peritonitis                                                                    Hemagglutinating                                                               encephalomyelitis                                                              Human coronavirus                                                              Infectious bronchitis                                                          Mouse hepatitis virus                                                          Rabbit coronavirus                                                             Rat coronavirus                                                                Sialodacryoadenitis virus                                                      Transmissible                                                                  gastroenteritis                                                                Turkey enteritis                                                               coronavirus                                                                    FLAVIVIRUSES                                                                   Banzi                                                                          Bukalasa                                                                       Bussuquara                                                                     Cowbone ridge                                                                  Dakar bat                                                                      Dengue Types 1-4                                                               Edge Hill                                                                      Entebbe bat                                                                    Ilheus                                                                         Japanese encephalitis                                                          Kokobera                                                                       Kyasanur                                                                       Louping III                                                                    Modoc                                                                          Montana myotis                                                                 leukoencephalitis                                                              Murray Valley encephalitis                                                     Ntaya                                                                          Powassan                                                                       Rio Bravo                                                                      Russian spring-summer                                                          encephalitis                                                                   Sepik                                                                          Simian hemorrhagic fever                                                       St. Louis encephalitis                                                         Stratford                                                                      Tenbusu                                                                        Uganda S                                                                       West Nile                                                                      Yellow fever                                                                   Zika                                                                           HERPESVIRUSES                                                                  Avian laryngotracheitis                                                        Duck enteritis                                                                 Falcon herpesvirus                                                             Lake Victoria cormorant                                                        Marek's disease                                                                Parrot herpesvirus                                                             Pigeon herpesvirus                                                             Turkey herpesvirus                                                             Bovine herpesvirus                                                             Infectious bovine                                                              rhinotracheitis                                                                Canine herpesvirus                                                             Equine cytomegalovirus                                                         Equine herpesvirus                                                             Feline herpesvirus                                                             Feline rhinotracheitis virus                                                   Channel catfish                                                                Herpesvirus salmonis                                                           Guinea pig herpes-like virus                                                   Guinea pig salivary gland                                                      virus                                                                          Guinea pig X virus                                                             Burkitt's lymphoma                                                             Cytomegalovirus                                                                Herpes simplex Types 1 & 2                                                     Varicella                                                                      Varicella-Zoster                                                               B Virus                                                                        Hepatitis A, B & C virus                                                       Herpesvirus aotus                                                              Herpesvirus ateles                                                             Herpesvirus saguinus                                                           Herpesvirus saimiri                                                            Monkey cytomegalovirus                                                         Simian herpesvirus 2 & 3                                                       Squirrel monkey                                                                cytomegalovirus                                                                Pseudorabies                                                                   Caprine herpesvirus                                                            Frog Virus 4                                                                   Mouse Salivary Gland Virus                                                     Rabbit herpesvirus                                                             ORBIVIRUSES                                                                    Bluetongue all types                                                           Changuinola                                                                    Colorado tick fever                                                            Corriparta                                                                     Epizootic hemorrhagic                                                          disease of deer                                                                Ieri                                                                           Irituia                                                                        Lebombo                                                                        Tribec                                                                         Wad Medani                                                                     ORTHOMYXOVIRUSES                                                               Avian Influenza                                                                Horse Influenza A                                                              Human Influenza                                                                A, B & C                                                                       Swine Influenza                                                                Thogoto                                                                        PAPOVAVIRUSES                                                                  Human polyoma                                                                  Bovine papilloma                                                               Human papilloma                                                                JC virus                                                                       K-virus                                                                        Lymphotropic Papovavirus                                                       Papilloma                                                                      Polyoma                                                                        Simian Papovavirus                                                             SV-40                                                                          PARAMYXOVIRUSES                                                                Bluegill                                                                       Bovine morbillivirus-like                                                      Bovine respiratory                                                             syncytial virus                                                                Canine distemper                                                               Canine parainfluenza                                                           Fer de Lance virus                                                             Measles                                                                        Mumps                                                                          Nariva                                                                         Newcastle disease                                                              Parainfluenza                                                                  Pneumonia virus of mice                                                        Respiratory syncytial                                                          Simian paramyxovirus                                                           Subacute sclerosing                                                            panencephalitis                                                                Yucaipa                                                                        PARVOVIRUSES                                                                   Adeno-associated virus                                                         Aleutian disease                                                               Avian adeno-associated                                                         Bovine parvovirus                                                              Canine parvovirus                                                              Feline panleukopenia                                                           Hemorrhagic encephalopathy                                                     Porcine parvovirus                                                             PICORNAVIRUSES                                                                 Poliovirus 1, 2 & 3                                                            Coxsackievirus, all types                                                      Echovirus, all types                                                           Enterovirus, all types                                                         Human rhinovirus, all types                                                    Avian encephalomyelitis                                                        Baboon enterovirus                                                             Bovine enterovirus,                                                            all types                                                                      Bovine rhinovirus,                                                             all types                                                                      Encephalomyocarditis                                                           Mouse encephalomyelitis                                                        Porcine enterovirus,                                                           all types                                                                      Rat encephalomyelitis                                                          Simian picornavirus,                                                           all types                                                                      POXVIRUSES                                                                     Alastrim (Variola minor)                                                       Bovine papular stomatitis                                                      Canary pox                                                                     Cotia                                                                          Cowpox                                                                         Embu                                                                           Fibroma                                                                        Fowlpox                                                                        Milker's nodule virus                                                          Monkeypox                                                                      Myxoma                                                                         Rabbit fibroma                                                                 Rabbitpox                                                                      Raccoonpox                                                                     Smallpox                                                                       Swine pox pox                                                                  Tanapox                                                                        Vaccinia                                                                       Yabu tumor poxvirus                                                            REOVIRUSES                                                                     Avian reovirus, all types                                                      Feline reovirus                                                                Reovirus, all types                                                            Turkey enteric reovirus                                                        RETROVIRUSES                                                                   Avian leukosis-sarcoma                                                         complex                                                                        Avian reticuloendotheliosis                                                    group                                                                          Feline leukemia group                                                          Murine leukemia-sarcoma                                                        group                                                                          Bovine syncytial virus                                                         Caprine arthritis-                                                             encephalitis virus                                                             Feline syncytia-forming                                                        Human T-cell lukemia virus                                                     Human immunodeficiency                                                         virus                                                                          Mouse mammary tumor                                                            Simian foamyvirus                                                              Squirrel monkey retrovirus                                                     Syncytium-forming virus                                                        of Marmosets                                                                   Visna virus                                                                    RHABDOVIRUSES                                                                  Aruac                                                                          Bovine paralytic rabies                                                        Chaco                                                                          Chandipura                                                                     Cocal virus                                                                    Hart virus                                                                     Infectious hematopoietic                                                       necrosis                                                                       Jurona                                                                         Kern Canyon                                                                    Klamath                                                                        Kwatta                                                                         Lagos bat                                                                      March                                                                          Mokola                                                                         Mossuril                                                                       Mount Elgon bat                                                                Navorro                                                                        Piry virus                                                                     Rabies                                                                         Sawgrass                                                                       Timbo                                                                          Vesicular stomatitis                                                           ROTAVIRUSES                                                                    Bovine rotavirus                                                               Calf rotavirus                                                                 Human rotavirus                                                                Porcine pararotavirus                                                          Porcine rotavirus                                                              Rhesus rotavirus                                                               Simian rotavirus                                                               TOGAVIRUSES                                                                    Alphavirus group                                                               Pestiviruses                                                                   Rubeviruses                                                                    UNCLASSIFIED VIRUSES                                                           Anaplasma marginale                                                            Creutzfeldt-Jakob                                                              Duck hepatitis                                                                 Eretmapodites                                                                  Equine infectious anemia                                                       virus                                                                          Frog virus 3                                                                   Golden shine virus                                                             Grunt fin agent                                                                Hepatitis A virus                                                              Hepatitis B virus                                                              Ichampadi                                                                      Infectious bursal disease of                                                   chickens                                                                       Infectious pancreatic                                                          necrosis of trout                                                              Infectious pancreatic                                                          necrosis virus                                                                 Kuru                                                                           Lymphocystis                                                                   Matucare                                                                       Nodamura virus                                                                 Quaranfil                                                                      Tadpole edema virus                                                            Tembe                                                                          Venkatapuram                                                                   Wanowrie                                                                       PLANT VIRUSES                                                                  Agropyron Mosaic                                                               Alfalfa Mosaic                                                                 Apple Chlorotic                                                                Apple Mosaic                                                                   Artichoke Latent                                                               Barley Stripe Mosaic                                                           Barley Yellow Dwarf                                                            Bean Common Mosaic                                                             Bean Golden Mosaic                                                             Bean Pod Mottle                                                                Bearded Iris Mosaic                                                            Beet Curly Top                                                                 Beet Mosaic                                                                    Beet Western Yellows                                                           Belladonna Mottle                                                              Bidens Mottle                                                                  Broad Bean                                                                     Broccoli Necrotic                                                              Carnation Mottle                                                               Cherry Leaf Rool                                                               Chrysanthemum Aspermy                                                          Citrange Stunt                                                                 Cowpea Chlorotic Mottle                                                        Desmodium Yellow Mottle                                                        Elm Mosaic                                                                     Glycine Mottle                                                                 Grapevine Fanleaf                                                              Henbane Mosaic                                                                 Lettuce Mosaic                                                                 Lychnis Ringspot                                                               Maize rough Dwarf                                                              Myrobalan Latent Ringspot                                                      Nasturtium Ringspot                                                            Oat Blue Dwarf                                                                 Onion Yellow Dwarf                                                             Pangola Stunt                                                                  Panicum Mosaic                                                                 Passionfruit Woodiness                                                         Peanut Stunt                                                                   Plantago Mottle                                                                Poa Semilatent                                                                 Pokeweed Mosaic                                                                Prunus Necrotic Ringspot                                                       Raspberry Bushy Dwarf                                                          Scophularia Mottle                                                             Tobacco Mosaic                                                                 Tomato Aspermy                                                                 Tulip Breaking                                                                 Watermelon Mosaic                                                              White Clover Mosaic                                                            Wound Tumor                                                            ______________________________________                                    

                  TABLE II                                                         ______________________________________                                                   MISCELLANEOUS ORGANISMS                                              ______________________________________                                                   Chlamydia psittaci                                                             Chlamydia trachomatis                                                          Coxiella burneti                                                               Ehrlichia risticii                                                             Rickettsia akari                                                               Richettsia canada                                                              Rickettsia conori                                                              Rickettsia montana                                                             Rickettsia mooseri                                                             Rickettsia prowazeki                                                           Rickettsia rickettsii                                                          Rickettsia sennetsu                                                            Rickettsia tsutsugamushi                                                       Rochalimaea quintana                                                           Rochalimaea vinsonii                                                           Thai tick typhus                                                               Wolbachia persica                                                    ______________________________________                                    

                  TABLE III                                                        ______________________________________                                         GRAM NEGATIVE BACTERIA                                                         ______________________________________                                         Acetobacter acet  Flavobacterium                                               Acholeplasma laidlawii                                                                           meningosepticum                                              Achromobacter viscosus                                                                           Francisella tularensis                                       Acidiphilium cryptum                                                                             Fusobacterium necrophorum                                    Acinetobacter calcoaceticus                                                                      Gardnerella vaginalis                                        Acinetobacter anatratus                                                                          Haemophilus aegyptius                                        Acinetobacter lwoffii                                                                            Hafnia alvei                                                 Actinomyces bovis Klegsiella oxytoca                                           Actinomyces israelii                                                                             Klebsiella pneumoniae                                        Actinomyces pyogenes                                                                             Legionella cherrii                                           Actinoplanes violaceus                                                                           Legionella feelei                                            Aeromonas hydrophila                                                                             Legionella pneumophila                                       Aeromonas salmonicida                                                                            Leptospira biflexa                                           Agrobacterium tumefaciens                                                                        Moraxella phenylpyruvica                                     Alcalicenes denitrificans                                                                        Morganella morganii                                          Alcaligenes faecalis                                                                             Mycoplasma canis                                             Anaerorhabdus furcosus                                                                           Mycoplasma hyorhinis                                         Aquaspirillum anulus                                                                             Mycoplasma pneumoniae                                        Arachnia propionica                                                                              Neisseria gonorrhoea                                         Arthrobacter ilicis                                                                              Neisseria meningitidis                                       Azotobacter beijerinckii                                                                         Oligella urethralis                                          Bacteroides bivius                                                                               Pasteurella multocida                                        Bacteroides fragilis                                                                             Proteus mirabilis                                            Bacteroides levii Proteus vulgaris                                             Bdellovibrio solpii                                                                              Providencia rettgeri                                         Beggiatoa alba    Providencia rustigianii                                      Beijerinckia indica                                                                              Providencia stuartii                                         Bifidobacterium boum                                                                             Pseudomonas aeruginosa                                       Bordetella bronchiseptica                                                                        Pseudomonas avenae                                           Bordetella pertussis                                                                             Pseudomonas cepacia                                          Borrelia burgdorferi                                                                             Pseudomonas pseudomallei                                     Brucella abortus  Pseudomonas putida                                           Cannylobacter coli                                                                               Salmonella choleraesuis                                      Campylobacter jejuni                                                                             Salmonelia typhi                                             Campylobacter pylori                                                                             Salmonelia typhimurium                                       Chlamydia psittaci                                                                               Serratia liquefaciens                                        Chlamydia trachomatis                                                                            Serratia marcescens                                          Chromobacterium violaceum                                                                        Shigella boydi                                               Citrobacter freundii                                                                             Shigella dysenteriae                                         Comamonas terrigena                                                                              Shigella flexneri                                            Deleva aesta      Shigella sonnei                                              Deleva venusta    Thiobacillus thiooxidans                                     Dermatophilus congolensis                                                                        Treponema hyodysenteriae                                     Edwardsiella tarda                                                                               Treponema pallidum                                           Eikenella corrodens                                                                              Ureaplasma gallorale                                         Enterobacter aerogenes                                                                           Veillonella caviae                                           Enterococcus avium                                                                               Vibrio cholerae                                              Enterococcus faecalis                                                                            Wolinella succinogenes                                       Enterobacter cloacae                                                                             Xanthobacter flavus                                          Erwinia citreus   Xanthomonas campestris                                       Escherichia coli  Yersinia pestis                                              Ewingella americana                                                                              Zymomonas mobilis                                            ______________________________________                                    

                  TABLE IV                                                         ______________________________________                                         GRAM POSITIVE BACTERIA                                                         ______________________________________                                         Deinococcus erythromyxa                                                                          Mycobacterium bovis                                          Deinococcus proteolyticus                                                                        Mycobacterium fortuitum                                      Erysipelothrix insidiosa                                                                         Mycobacterium                                                Erysipelothrix rhusiopathiae                                                                     intracellulare                                               Eubacterium aerofaciens                                                                          Mycobacterium leprae                                         Eubacterium angustum                                                                             Mycobacterium tuberculosis                                   Eubacterium combesii                                                                             Norcardia asteroides                                         Eubacterium eligens                                                                              Norcardia brasiliensis                                       Eubacterium fossor                                                                               Paracoccus denitrificans                                     Jonesia denitrificans                                                                            Pediococcus dextrinicus                                      Kurthia gibsonii  Peptostreptococcus                                           Lactobacillus agilis                                                                             asaccharolyticus                                             Lactobacillus brevis                                                                             Peptostreptococcus micros                                    Lactobacillus buchneri                                                                           Phormidium sp                                                Lactobacillus carnis                                                                             Planococcus citreus                                          Lactobacillus casei                                                                              Propionibacterium acnes                                      Lactobacillus divergens                                                                          Propionibacterium                                            Lactobacillus helveticus                                                                         freudenreichii                                               Lactobacillus jensenii                                                                           Rhodococcus equi                                             Lactobacillus kefir                                                                              Rhodococcus erythropolis                                     Lactobacillus xylosis                                                                            Sarcina maxima                                               Lactococcus garviae                                                                              Staphylococcus aureus                                        Lactococcus lactis                                                                               Staphylococcus epidermidis                                   Lactococcus plantarum                                                                            Staphylococcus hominis                                       Leptothrix buccalis                                                                              Staphylococcus warneri                                       Leuconostoc lactis                                                                               Stomatococcus                                                Leuconostoc mesenteroides                                                                        mucilaginosus                                                Leuconostoc oenos Streptobacillus                                              Listeria grayi    moniliformis                                                 Listeria innocua  Streptococcus dysgalactiae                                   Listeria monocytogenes                                                                           Streptococcus equi                                           Micrococcus agilis                                                                               Streptococcus equisimilus                                    Micrococcus cryophilus                                                                           Streptococcus faecalis                                       Micrococcus halobius                                                                             Streptococcus pyogenes                                       Micrococcus luteus                                                                               Streptomyces albulus                                         Mycobacterium aurum                                                                              Streptomyces vulgaris                                        Mycobacterium avium                                                            ______________________________________                                    

                  TABLE V                                                          ______________________________________                                         GRAM POSITIVE SPORE FORMING BACTERIA                                           Bacillus            Clostridium                                                ______________________________________                                         acidocaldarium      acetobutylicum                                             alcalophilus        acidiurici                                                 alvei               aerotolerans                                               aminoglucosidicus   barkeri                                                    aneurinolyticus     beijerinckii                                               anthracis           bifermentans                                               badius              botulium                                                   brevis              cadaveris                                                  capitovalis         carnis                                                     cereus              cellulolyticum                                             chitinosporus       chauvoei                                                   circulans           clostridiiforme                                            cirroflagellosus    coccoides                                                  coagulans           collagenovorans                                            epiphytus           cylindrosporum                                             fastidiosus         difficile                                                  filicolonicus       durum                                                      firmus              flavum                                                     freudenreichii      formicoaceticum                                            fructosus           haemolyticum                                               globigii            hastiforme                                                 globisporus         histolyticum                                               gordonae            indolis                                                    implexus            kaneboi                                                    insolitus           kluyveri                                                   laevolacticus       lentoputrescens                                            larvae              limosum                                                    laterosporus        lortetii                                                   lentimorbus         perfringens                                                lentus              putrificum                                                 licheniformis       septicum                                                   megaterium          sordellii                                                  mycoides            sporogenes                                                 pumilus             tetani                                                     schlegelii          tetanomorphum                                              stearothermophilus  thermocellum                                               subtilis            thermolacticum                                             thuringiensis       tyrobutyricum                                              xerothermodurans    villosum                                                   ______________________________________                                    

                  TABLE VI                                                         ______________________________________                                         FUNGI                                                                          ______________________________________                                         Absidia blakesleeana                                                                             Entonaema liguescens                                         Achaetomium luteum                                                                               Epidermophyton floccosum                                     Achlya hyrogyna   Filobasidiella neoformans                                    Aciculoconidium aculeatum                                                                        Fonsecaea pedrosoi                                           Acladium castellanii                                                                             Fusarium solani                                              Acemoniella lutzi Geotrichum candidum                                          Acrodontium salmoneum                                                                            Gibberella baccata                                           Actinodendron verticillatum                                                                      Gymnosporangium globosum                                     Actinomucor elegans                                                                              Histoplasma capsulatum                                       Acytostelium elipticum                                                                           Kluyveromyces wickerhamii                                    Agaricus abruptibulbus                                                                           Madurella mycetomi                                           Agaricus campestris                                                                              Melampsora medusae                                           Akenomyces costatus                                                                              Microsporum canis                                            Alternaria alternata                                                                             Mucor hiemalis                                               Alternaria citri  Nectriella pironii                                           Armillaria limonea                                                                               Neurospora tetrasperma                                       Arthrobotrys oligospora                                                                          Paecilomyces lilacinus                                       Arthroderma benhamiae                                                                            Penicillium aurantiogriseum                                  Arthroderma gypseum                                                                              Phialophora richardsiae                                      Arthroderma incurvatum                                                                           Phycomyces nitens                                            Articulospora tetracladia                                                                        Pichia membranaefaciens                                      Aspergillus carneus                                                                              Pityrosporium ovale                                          Aspergilius fischeri                                                                             Pseudallescheria boydii                                      Aspergillus fumigatus                                                                            Puccinia graminis                                            Asperaillus niger Pyrenophora trichostoma                                      Aureobasidium mansonii                                                                           Rhizoctonia repens                                           Basidiobolus hantosporus                                                                         Rhizomucor pusillus                                          Blastobotrys aristata                                                                            Rhizopus microsporus                                         Blastomyces dermatitidis                                                                         Rhodotorula rubra                                            Blastoschizomyces capitatus                                                                      Rhynchosporium secalis                                       Botrytis squamosa Saccharomyces cerevisiae                                     Byssochlamys fulva                                                                               Sclerotium rolfsii                                           Candida albicans  Sporothrix schenckii                                         Candida tropicalis                                                                               Sporotrichum thermophile                                     Cephalosporium deformans                                                                         Stemphylium botryosum                                        Ceratocytis ulmi  Torula thermophila                                           Chaetomium globosum                                                                              Torulopsis pintolopesii                                      Chrysosporium pannorum                                                                           Trichoderma polysporum                                       Cladosporium carrophilum                                                                         Trichophyton mentagrophytes                                  Cladosporium resinae                                                                             Trichophyton rubrum                                          Coccidioides immitis                                                                             Ulocladium botrytis                                          Cronartium fusiforme                                                                             Uromyces phaseoli                                            Cryptococcus neoformans                                                                          Verticillium nigrescens                                      Curvularia prasadii                                                                              Xylohypha bantiana                                           Dictyostelium discoideum                                                                         Yarrowia lipolytica                                                            Zygosaccharomyces bailii                                     ______________________________________                                    

                  TABLE VII                                                        ______________________________________                                         PROTISTS - ALGAE/PROTOZOA                                                      ______________________________________                                         Acanthamoeba astronyxis                                                                          Leishmania hertigi                                           A. castellanii    Leishmania mexicana                                          A. culbertsoni    Leishmania tropica                                           A. hatchetti      Leptomonas pyrrhocoris                                       A. lenticulata    Lingulamoeba leei                                            A. polyphaga      Lohomonas piriformis                                         A. royreba        Monocercomonas colubrorum                                    Babesia microti   Muriella aurantiaca                                          Botrydium cystosum                                                                               Naegleria australiensis                                      Cephaleuros virescens                                                                            Naegleria fowleri                                            Chlamydomonas dorsoventralis                                                                     Naectieria gruberi                                           Chlorella protothecoides                                                                         Naectieria jadini                                            Chlorella saccharophilia                                                                         Nosema necatrix                                              Chlorella sorokiniana                                                                            Ochromonas malhamensis                                       Chlorella variegata                                                                              Paramecium primaurelia                                       Chlorella xanthella                                                                              Paramecium                                                   Chlorella zopfingiensis                                                                          multimicronucleatum                                          Chlorogonium elongatum                                                                           Pentatrichoimonas hominis                                    Crithidia fasciculata                                                                            Plasmadium brasilianum                                       Dientamoeba fragilis                                                                             Plasmodium coatneyi                                          Dunaliella tertiolecta                                                                           Plasmodium cynomolgi                                         Entamoeba coli    Plasmodium falciparum                                        Entamoeba gingivalis                                                                             Plasmodium vivax                                             Entamoeba histolytica                                                                            Prototheca wickerhamii                                       Euglena gracilis  Tetracystis disociata                                        Giardia intestinalis                                                                             Tetrahymena borealis                                         Giardia lamblia   Tetrahymena thermophila                                      Haematococcus lacustris                                                                          Trichomonas gallinae                                         Hartmannella limax                                                                               Trichomonas vaginalis                                        Herpetomonas mariadeanei                                                                         Tritrichomonas foetus                                        Leishmania braziliensis                                                                          Trypanosoma brucei                                           Leishmania donovani                                                                              Trypanosoma cruzi                                            ______________________________________                                     

We claim:
 1. A biocidal, aqueous, composition for killing bacteria, spores, fungi, and viruses on nonabsorbent surface comprising:a) two heterocyclic quaternary ammonium compounds, each in the amount of from about 0.05 to 3 percent by weight; b) one heterocyclic dialdehyde containing up to 6 carbon atoms in the amount of from about 0.5 to about 7 percent by weight; and c) at least one aliphatic hydroxyl compound having from 1 to 8 carbon atoms in the amount from 0.1 to about 3 percent by weight;all weight percents being in the final use dilution.
 2. The biocidal composition of claim 1, wherein the weight percent of the heterocyclic dialdehyde in the final use dilution is in the amount of from about 2.6 to about 5 weight percent.
 3. The biocidal composition of claim 1, further comprising a chelating agent in the amount of zero to about 0.025 weight percent of the final use dilution.
 4. The biocidal composition of claim 3, wherein the chelating agent is tetrasodium ethylenediamine tetraacetate.
 5. The biocidal composition of claim 1, wherein the dialdehyde is furan-2,5-dialdehyde comprising from 2.6 to 3.2 weight percent of the final use dilution.
 6. The biocidal composition of claim 1, wherein the heterocyclic quaternary ammonium compound contains an aromatic moiety.
 7. The biocidal composition of claim 1, wherein one of the heterocyclic quaternary ammonium compounds is n-hexylpyridinium halide.
 8. The biocidal composition of claim 1, wherein both of the heterocyclic quaternary ammonium compounds are the same.
 9. The biocidal composition of claim 1, wherein the aliphatic hydroxyl compound is selected from the group consisting of isopropyl alcohol, propylene glycol, and their mixtures.
 10. The biocidal composition of claim 1, further comprising a soluble, inorganic, nitrite salt.
 11. The biocidal composition of claim 1, wherein all the all the quaternary ammonium compounds are halide salts.
 12. A method for sterilizing a nonabsorbent surface comprising the steps of contacting said surface with an effective sterilizing amount of an aqueous composition comprising:a) two heterocyclic quaternary ammonium compounds, each in the amount of from about 0.05 to 3 percent by weight; b) one heterocyclic dialdehyde containing up to 6 carbon atoms in the amount of from about 0.5 to about 7 percent by weight; and c) at least one aliphatic hydroxyl compound having from one to eight carbon atoms in the amount from about 0.1 to about 3 percent by weight;all weight percents being in the final use dilution; and killing on said surface bacteria, spores, fungi, and viruses. 